Microporous Porphyrin‐Based Metal Carboxylate Frameworks with Various Accessible Metal Sites: [Cu₂(MDDCPP)] [M = Zn²⁺, Ni²⁺, Pd²⁺, Mn³⁺(NO₃), Ru²⁺(CO)]

We successfully synthesized a series of porphyrin‐based metal carboxylate frameworks with the composition [Cu 2 (MDDCPP)] [M = Zn 2+ , Ni 2+ , Pd 2+ , Mn 3+ (NO 3 ), Ru 2+ (CO)] using MDDCPP [M = Zn 2+ , Ni 2+ , Pd 2+ , Mn 3+ Cl, Ru 2+ (CO)] building blocks. Single‐crystal X‐ray analysis revealed that the framework of [Cu 2 (ZnDDCPP)] formed a three‐dimensional network with (6 2 · 8 2 · 10 2 )(6 2 · 8) 2 topology, consisted of a two‐component linkage (i.e., paddlewheel Cu 2 nodes and ZnDDCPP building blocks), and possessed an internal spherical cavity with a diameter of ca. 20 Å. This internal cavity was surrounded by a total of 16 accessible metal sites (AMSs) with two distinct metals, i.e., eight Zn atoms from the ZnDDCPP units and eight Cu atoms from the paddlewheel units. X‐ray powder diffraction measurements revealed that five complexes were isostructural regardless of the identity in the central metal of the DDCPP unit, and the diffraction patterns closely matched a pattern simulated from single‐crystal data for [Cu 2 (ZnDDCPP)]. This suggested that a wide variety of AMSs could be incorporated into the framework without alteration of the framework topology. The [Cu 2 (MDDCPP)] series exhibited permanent porosity, with BET surface areas in the range 379–810 m 2 g –1 , and adsorbed between 0.55 and 1.16 wt.‐% H 2 at 77 K and 0.1 MPa.